Fluorinated hydrocarbon polymers and preparation thereof



3,033,238 Patented Mar. 26, 1963 3,383,238 FLUGRENATED HYDRA CAREEGN PGLYlviERS AND PREPARA'HGN THEEEBF Murray Hanptschein, Glenside, and Miiton Braid, Philadelphia, Pa, and Francis trawler, Mesa, Ariz., assignors to Pennsalt Chemicals Corporation, Philadelphia, Pa., a corporation of Pennsylvania N Drawing. Filed Dec. 11, 1957, Ser. No. 701,995 11 Claims. (Ci. Edd-648) This invention relates to a new method for producing polymers of certain unsaturated fluorinated organic compounds and to novel polymeric products made thereby.

This application is a continuation-in-part of our copending application Serial No. 614,821, filed October 9, 1956, now abandoned.

In recent years, interest in lluorine containing polymeric materials has been intense. Basically, highly fiuorinated polymeric materials are desirable because they are more stable to heat and chemical reagents than similar, nonfiuorinated materials. Fluorinated polymers have been used in many different applications where high heat or chemical resistance is required, for example as dielectrics, fire extinguishers, heat transfer media, solvents, lubricants, plasticizers, coolants, gaskets and valve pachings, and protective coatings.

One of the obstacles to the more extensive use of fluoropolymers has been that they are difiicult and expensive to prepare. Many potentially attractive fluorocarbon monomers polymerize only under very rigorous con ditions or only to a slight extent, e.g. to the dimer or trimer. With still others, it has not been possible to obtain any polymerization at all.

It has been proposed to overcome this difficulty by copolymerizing ditficultly polymerizable monomers with monomers known to polymerize more readily. Thus, perfiuoropropene has been copolymerized with ethylenically unsaturated hydrocarbons. In such copolymerization reactions, however, extraneous molecules are introduced into the polymer chain, so that all the properties of the homopolymer are not realized.

It has also been attempted to use the *tclomcrization" technique to achieve polymeric fiuorocarbons. Thus Haszeldine (Journal of the Chemical Society 3559 [1953]) describes a classic tclomerization reaction between CF I and CF CF to give CF (CF CF I where It may be as high as 20. This tclomerization reaction is said to build up large molecules by the following rapid chain reaction mechanism.

(1) heat or CF 1 GF I light CFs-CFr-CF 72(GF2:CF2) CF (GFgCF2)n+t' In this mechanism the telomer chain is built up by almost instantaneous reaction between the growing telomer radical and successive molecules of olefin. The molecular size of the final product is in general independent of the time of reaction, but rather is dependent on the probability of a growing telomer radical meeting and reacting with a telogen molecule to effect chain termination, and therefore on the proportions of olefin and tclogen used.

The particular reaction referred to above gave relatively high telomers of tetrailuoroethylene, but when an attempt was made to apply it to perfluoropropene, a more ditficultly polymerizable monomer, using ultra-violet light as the initiating agency, no telomers were obtained having more than 2 olefin units, with nearly all the product being the 1:1 adduct, 2-iodoperfiuorobutane (Haszeldine, Journal of the Chemical Society 3559 [1953]).

From these facts it could be concluded that with certain classes of unsaturated fluorinated compounds, namely with those compounds which would not readily undergo homopolymerization, telomers having more than about two units could not be formed. Attempts to force the telomer to accept more units were thought inevitably to lead to disproportionation, dimerization or internal expulsion of halogen.

It is an object of the present invention to provide a method whereby unsaturated fluorinated compounds, hitherto considered difficult or impossible to polymerize or telomerize may be built up into comparatively large molecules.

It is a further object of the invention to provide a method for making certain fluorinated polymers which is simpler and more easily controlled than methods hitherto known.

It is a further object of the invention to provide a method whereby tluorinated telomers having a specific desired molecular weight can be obtained in good yield.

It is a further object of the invention to provide novel Huorinated polymeric compounds from monomeric materials hitherto considered difiicult or impossible to polymerize.

These and other objects are accomplished according to the invention, by heating at between about C. and about 350 C. a telogen having the general formula where Q is selected from the group consisting of bromine and iodine, and where R is selected from the group consisting of (a) periluoroaliryl, perfluorocycloalkyl and pertluoroalsenyl radicals; and pertluorochloroalkyl, perfiuorochiorocycloalkyl, perfiuorohydrocycloalkyl, perfluorochioroalkenyi and perlluorohydroalkenyl radicals in which the carbon atom which is attached to the Q atom has at least one substituent selected from the group consisting of fluorine, pertluoroalkyl radicals, and R"CF radicals where R" is a perfiuorochioroalkyl or a perfiuorohydroalkyl radical, and (b) groups having the gen eral formula R'CXY where R is selected from the group consisting of fluorine, alkyl, aryl and aralkyl radicals; and halogenoalkyl, halogcnoaryl and halogenoaralkyl radicals having not more than one iodine atom, and where X and Y are selected from the group consisting of fluorine, and perfiuoroalkyl and RCF radicals each having up to about 5 carbon atoms, hydrogen, chlorine and bromine, provided that when X is selected from the group consisting of chlorine and bromine, Y is selected from the group consisting of fluorine, hydrogen, and periluoroalkyl and RCF radicals having up to about 5 carbon atoms; provided further that when X is selected from the group consisting of chlorine and bromine and Y is selected from the group consisting of fluorine, hydrogen, and pertluoroalkyl and R"CF radicals having up to about 5 carbon atoms, R is selected from the group consist ing of fluorine, and halogenoalkyl and halogenoaralkyl radicals having not more than one iodine atom and in which the carbon atom which is attached to the CXY linkage has two substituents selected from the group consisting of fluorine, chlorine, perlluoroalkyl radicals having not more than about 5 carbon atoms and R"CF radicals having not more than about 5 carbon atoms, and has not more than one chlorine atom subtended therefrom; and provided still further that X and Y are not both hydrogen, with at least an equimolar proportion of an unsaturated, fluorinated, diflicultly polymerizable compound.

As indicated above, unsaturated fluorinated difficultly polymerizable compounds are recognized by the art as comprising a particular group. For purposes of the present description and the claims appended hereto, they may be further defined as those fiuorinated, unsaturated compounds which do not undergo substantial homopolymerization in the presence of a peroxide initiator at the temperature at which the initiator breaks down to form free radicals, for example, at less than 130 C. Some typical peroxide initiators are benzoyl peroxide, di-tertiarybutyl peroxide, and acetyl peroxide.

The fluorinated unsaturated compounds which are useful in the present invention are further characterized in that the product obtained by reaction with the telogen,

Q U designating the fluorinated unsaturated difficultly polymerizable compound, and n being an integer from say 1 to 20, conforms to the definition given above for the telogen.

In the present state of knowledge it is dilficult if not impossible to define the fluorinated unsaturated compounds rigorously by any simple structural characteristics. However, the following structure covers many of them:

where (a) R; is selected from the group consisting of F and H.

(b) R is selected from the group consisting of F, H and -CF R is selected from the group consisting of F, -CF Cl and -CF;,, provided that when R; and R are both F, R may also be H; and

(:1) R is CF R,, where R, is selected from the group consisting of F, Cl, alkyl having up to about 8 carbon atoms, halogenoalkyl having up to about 8 carbon atoms and not more than one iodine atom, aryl, halogenoaryl having not more than I iodine atom, aralkyl having up to about 5 carbon atoms in the alkyl group, and halogenoaralkyl having up to about 5 carbon atoms in the alkyl group and not more than one iodine atom; provided that (e) When both R and R are H or F, and R is F, or CF R; can be -CF Br, CF I or -CF R (1) When R is H or F, R is F and R is -CF R,,, R may be Cl or Br;

(g) When R and R are P, R and R taken together may constitute a cyclic perfluoromethylene, pertluorochloromethylene or perfluorohydromethylene chain having from 2 to 4 carbon atoms;

(It) When any two of R R and R are F and the other is H, F or Cl; R may be a perfiuoroalkenyl, perfluorochloroalkenyl or perfluorohydroalkenyl radical hav ing up to about 8 carbon atoms;

(i) When R R and R are all F, R, may be alkyl having up to about 8 carbon atoms, halogenoalkyl having not more than one iodine atom and up to about 8 carbon atoms, halogenoaryl having not more than one iodine atom, arulkyl having up to about 5 carbon atoms in the alkyl group and halogenoaralkyl having up to about 5 carbon atoms in the alkyl group and not more than one iodine atom;

(j) When both R and R are H or F and R is Cl, R may be CF R,,.

As used in the present specification, the prefix perfluoro means that the compound so described contains nothing but carbon and fluorine.

The term perfiuorochloro means that the compound so described contains only carbon, fluorine and chlorine and that the molar ratio of fluorine to chlorine is at least 1.

The term perfluorohydro means that the compound so described contains only carbon, hydrogen, and fluorine and that the molar ratio, fluorine to hydrogen is at least 1.

It has been found, surprisingly, that when the supposedly nonreactive fluoroolefins and fluoro diolefins of the class described are heated with telogens of the type defined above at the temperatures indicated, reaction occurs with relative ease to give high molecular weight products.

Most of the compounds have not been made hitherto and the invention therefore includes, as well as the method described, compounds having the general formula where R and U are as defined above, Q is a halogen atom and n is an integer from 1 to about 20, provided that when U is a perfluoropropene radical n is greater than 2. Certain other specific compounds are also considered to be within the scope of the broad invention.

As described more fully below, the initial compound where Q is bromine or iodine maybe stabilized by replacing the bromine or iodine with chlorine or fluorine by conventional procedures. In like manner an initial iodine compound may be converted to a bromine compound, if desired.

The mechanism of the reaction defined above is different from that postulated previously in connection with the telomerization of tetrafluoroethylene. Instead of chain propagation taking place through reaction between a growing telomer radical and successive molecules of olefin, as in reaction (3) above, step-wise addition takes place with the telomeric iodoor bromocompound being formed in each case.

In the present case, even in the presence of very large excesses of olefin, no evidence of free radical chain propagation was obtained, since after a short time the only product isolated was the 1:1 adduct. The 1:1 adduct is thus the precursor of the 2:1 adduct which in turn is the precursor of the 3:1 adduct, etc.

This is illustrated in the reaction of perfiuoropropyl iodide:

The maintenance of an energy level sufliciently high to promote and sustain the reaction is no doubt one of the principal reasons why telomers of unreactive olefins can be produced at appreciable rates by thermal synthesis in accordance with the present invention, but not by the photochemical or peroxide-induced initiation previously employed.

The class of diflicultly polymerizable unsaturated fluorinated compounds defined above as suitable for use in the present invention includes such specific compounds as CF: CF:

or CF I but like-Cm F: CF:

0 F=O F 0 HF-C F (E and ll Fr-CFa HF- F All these compounds are either impossible or very difficult to polymerize by peroxide or free radical initiation.

The telogens which may be used in the present invention include such specific compounds as CF I, C F I,

In some cases the telogen may be formed in situ, by the addition of, for example, 1;, K11, orBr to the unsaturated compound.

In general, the iodo compounds are preferred over the corresponding bromo compounds.

The reaction conditions will vary to some extent, depending on the particular reactants and the type of product desired.

The temperature should in general be between about 100 C. and about 350 C., preferably between about 160 and about 250 C. The reaction may be carried out at atmospheric pressure, but preferably high pressures are used, for example up to about 20,000 p.s.i.g. usually between about 500 p.s.i.g. and about 10,000 p.s.i.g.

With respect to the proportions of telogen and unsaturated compound used, for maximum yields of any desired telomer it is always necessary to use at least the stoichiometric amount of olefin required by the telomel' it is desired to produce, over the entire period of the reaction. Moreover, considered at any instant of time it is preferred to have at least an equimolar amount of unsaturated compound present. Preferably the proportion of unsaturated compound is between about 2 and about 20 times the molar amount of telogen and usually 6 between about 2 and about 10 times the molar amount of telogen.

The reaction time is not critical in the sense that it determines whether or not the reaction will go, but it is an important variable in determining the conversion obtained and the molecular size of the product. Since the reaction proceeds stepwise, i.e. the 1:1 adduct reacts with additional unsaturated compound to form the 1:2 adduct and so on, the reaction time for any desired chain length must be sufficient to permit the precursors to form and react. In general, the longer the reaction time, the greater the proportion of high molecular weight product obtained, and when a short reaction time is used, only low molecular weight product is obtained. In this the present process is clearly different from conventional telomerizations proceeding by free radical chain mechanism in which the chain length is determined primarily by the proportion of telogen or chain transfer agent used. Thus in prior art processes when an excess of olefin is present only high molecular weight products are obtained even with short reaction times.

In the present process the specific reaction time will depend on the particular reactants and on the efliciency of contact between them. In general, it will be from about 3 hours to 3-4 weeks, preferably from about 6 hours to 2 weeks.

Telomers made according to the invention will undergo a variety of other reactions. In many cases, for example, it is desirable to replace the Q atom (Br or I) with chlorine or fluorine to enhance the stability of the telomer. These replacements may be carried out by any conventional method, for example by reaction with elemental chlorine at a pressure of say atmospheric to 10,000 p.s.i.g. and at a temperature of say room temperature to 270 (3.; or by reaction with cobalt trifluoride at a temperature of say to 270 C.

Telomers made according to the present invention may also be stabilized by heating them at a temperature somewhat higher, e.g. 50200 higher, than the optimum temperature used in the formation of the telomer, for example at 200-550 C. By this procedure, the Q atom (Br or I) is removed, as Q and the stabilized products include coupled telomers of the general type Coupled products of this general class and the general methods for their manufacture are described in the copending application of R. N. Haszeldine, Serial No. 179,- 217 filed March 12, 1962; and in Patent No. 3,046,304 of R. N. Haszeldine. Application Serial No. 179,217, owned by the assignee of the present application, is a continuation of application Serial No. 680,924, filed August 29, 1957, which in turn was a continuation-inpart of application Serial No. 526,087, filed August 2, l955, and application Serial No. 377,716, filed August 31, 1953. Applications Serial Nos. 680,924, 526,087 and 377,716 have all now been abandoned.

The physical properties of the compounds obtained in accordance with the present invention vary with the starting compounds and the size of the product. The utility of the compound and its stabilized analogues, of course, varies with these properties.

In general, it may be said that compounds and particularly the stabilized analogues made in accordance with the present invention are suitable for the same applications in which similar, non-fiuorinated compounds are employed, with the added advantage that the fluorinated compounds have in general higher stability to heat and chemically attack. In addition, compounds of the present invention may be used in many instances where there is no parallel use of non-fiuorinated analogues.

Specifically, stabilized products made in accordance with the invention have high dielectric strength and are, therefore, useful as insulators and condenser fluids.

Those stabilized products which are oils provide superior hydraulic fluids and permanent lubricants for instruments. They are useful as mold release agents, and, in the laboratory, as stopcock lubricants. Their chemical and thermal stability makes them excellent heat transfer media and refrigerants. They can also be used to advantage as damping fluids in shock absorbers and the like.

Stabilized products made in accordance with the invention are further useful as ingredients for polishes and as water and oil repellent finishes for textiles. As specifically described below, they can be used as plasticizers for fiuoropolymers. In particular, it has been found that polytetrafluoroethylene can be plasticized by compounds boiling above 100 C. at atmospheric pressure and having the formula where n is an integer from 1 to about 20, R is selected from the group consisting of perfiuoroalkyl and perfluorochloroalkyl and X is selected from the group consisting of The lower telomers, i.e. where n is 1 and 2, such as CF Cl[CF CF(CF Cl, CF [CF CF(CF Br, CF Br[CF CF(CF Br and the like, are valuable as vapor phase coolants and dielectrics for electrical equipment and as vapor phase Coolants in processes where leaks in a coolant system would cause violent reactions if ordinary organic coolants were used. They are also useful as temperature differential fluids in thermometric devices.

The lower telomer iodides where n is up to about 5 avg. are especially useful as bactericidal and bacteriostatic. agents. Compounds such as act as iodine carriers and when applied to a surface will release iodine slowly, providing a long lasting potent germicidal barrier. They are particularly suited to use on the skin because the fluorocarbon portion of the molecule is inert and will not be absorbed. The telomers in which n is l or 2 are especially suitable for solution or lotion formulations in concentrations of 1:10 to 1:1000 and have the advantage of a high weight proportion of iodine. The telomers in which n is 3 to about 5 are use ful in salves and ointments.

The invention will be further described with reference to the following specific examples, it being understood that the examples are given for purposes of illustration only and are not to be taken as in any Way restricting the invention beyond the scope of the appended claims.

EXAMPLE I A 3 00 ml. Monel autoclave was charged with 98.0 g.

(0.331 mole) of l-iodoperfiuoropropane. After cooling in Dry Ice, 240 g. (1.6 moles) of perfiuoropropene were introduced by vacuum transfer. The autoclave was then closed and heated with shaking to about 200 C. for a period of four days. During this period the pressure dropped from 4600 p.s.i.g. to 2100 p.s.i.g., most of the drop occurring during the first day. There were recovered 157 g. perfiuoropropene and 6.7 g. l-iodoperiiuoropropane. The total of 176 g. of product was separated into individual telomer fractions by rectification. Con version was 88% based on moles of iodide converted to telomer.

These fractions were:

(a) C F [CF CF(CF )]I44 mole percent of total product. This fraction had a boiling point of 110 C. at 760 mm. and 62 C. at mm., and an index of refraction n =l.3284. Analysis showed F=55.4%; Calculated F=55.4%.

(b) C3F7[CF2CF(CF3)]2I-28 mole percent of total product. This fraction had a boiling point of 62 C. at 10 mm. and 104 C. at mm., and a refractive index ri :l.33l0. Analysis showed 0:180, F:60.5% by weight. Calculated for this telomer C=18.l, F=60.6% by weight.

(c) C F [CF CF(CF I-l6 mole percent of total product. This fraction had a boiling point of 101 C. at 10 mm. and a refractive index n =l.3340 and a molecular weight of 746. Analysis showed C=19.4, F- 63.6% by Weight. Calculated for this telomer C=l9.3, F=63.7% by weight.

(d) C F {CF CF(CF I8 mole percent of total product. This fraction had a boiling point of 83 C. at about 0.1 mm., indices of refraction n =l.3395, 1r :l.337. Analysis showed C=20.3, F=66.0% by weight. Calculated for this telomer C:20.l, F=65.7%.

(e) A fifth fraction was obtained in which the average value of n was 5. This constituted about 4 mole percent of the total product.

In carrying out the above procedures, precautions were taken to exclude oxygen.

EXAMPLES II TO X The procedure of Example I was carried out using different molar ratios of telogen to olefin. The results of these runs are compiled in Table I below and the properties of the products in Table II.

EXAMPLE XI The procedure of Example I was repeated, but the autoclave was repressured to 4700 p.s.i.g. after one day with perfluoropropene. A conversion comparable to that described in Example I was obtained in two days, i.e. 48 hours total reaction time.

EXAMPLE XII The procedure of Example I was carried out using Table l Pressure Percent yield Mole ratio Time Percent Example C3Fe/C3F7I (hrs) conver Initial Terminal sion n=1 n=2 n=3 n=4 n=5 71:7 n=10 avg avg avg.

2 1. 32 l 41 2,100 800 37 72 22 5 Z 1.30 88 2,000 1, 000 37 84 14 2 1. 51 64 2. 800 1. 200 50 68 22 10 2. 63 22 3, 600 2. 300 41 75 18 7 2. 75 42 5, 000 2, 900 57 63 22 15 4. 07 63 4, 700 2. 300 73 56 24 16 4. 26 112 3. 000 l, 300 84 65 21 13 4. S9 20 4, 600 3, 500 52 66 19 16 10. 4 336 4, 700 1, 900 94 7 11 41 1 Conversion of iodide to telomer.

I No shaking.

a,os3,2 3 8 Tab 1e II B .1 M01. weight Analysis perce at by weight C3F1(CF3CF)DI Ml. n1) Tomp., n1ax., Carbon Fluorine 0. Mm. C. *0. Cale. Found m Cale. Found Cale. Found 1. 3284 24 440 282 210 16. 2 55. 4 55. 4 7 IMO, 1. 3310 24 596 282 210 18. 1 1. 80 60. 6 3 00.

10 1. 3340 24 746 282 200 19. 3 19. 4 63. 7 63. (i Ca.0. 1 1.3395 19 806 282 190 20.1 20. 3 65. 7 66.0

l Ultraviolet Spectrum maxima in isooctnne, 2,3,Btrichlorohcptalluorobutano and 1,2,Mrichlorotrifiuorocthane.

4 Molar extinction coeliicient in isooctane. 3 Calc. for CnFmI: I, 21.29, Found: 21.1.

4 Kinematic viscosities in centistokcs: 190.5 (78. 1 F), 11.7 411.4" E),

5 Mol. weight calculated in the usual way from the absorbency (at chloroheptafluorobutane or 1,2,2-tricl1lorotrifluorocthanc.

' Solids at room temperature.

55 g. (0.338) mole) of iodine monochloride and 316 g. (2.11 moles) periluoropropene. The reactants were heated with shaking at 210215 C. for 30 hours and then at 225 C. for 167 hours. The observed pressure drop was 1900 p.s.i. The product (131 g.) was rectified to give the following fractions ranging from a light to a viscous oil to a solid:

Percent (a) Boiling point below 34 at 100 mm. (b) Boiling point below 35-100" at 100 mm 33 (0) Boiling point below 4067 at ca. 0.1 mm. 24 (d) Boiling point below 67-99" at ca. 0.1 mm. 9 (e) Boiling point 99 to above 132 at ca. 0.1 mm. 8 (f) Residue, M.P. 4l52 C. 1

Fractions (a) and (b) contained n=1 and 2. Fraction (b) had an average n value of 1.5. Fraction (0) had an average it of 3; fraction (:1) of 4; fraction (2) of 5; and the residue (F) of 7.

EXAMPLE XIII The telogen CF ClCF(CF )I is formed by heating ICl with CF CF=CF Using a molar ratio of telogen to olefin of about 1:10, this CF ClCF(CF )I is then heated with perfiuoropropene at 225 C. for about 150 hours. Telomers of the formula CF ClCF(CF3) ICF CF(CF ],,I

where n is from 1 to about 7 avg. are formed.

EXAMPLE XIV A Monel autoclave was charged with 27.6 grams of iodine and 202 grams of perfiuoropropene. The autoclave was heated with shaking at 200 to 250 for 300 hours. There was recovered approximately 155 grams of perfiuoropropene and 33 grams of material boiling above room temperature in vacuo were collected. The most volatile fraction boiled up to 53 at less than 0.1 mm.

The following three higher boiling fractions were isolated:

(1) A light oil, boiling at 5375 C. at less than 0.1 mm.

(2) A medium oil, boiling at 75105 at less than 0.1 mm.

(3) A low melting solid boiling at 105 to approximately 200 C. at less than 0.1 mm.

EXAMPLE XV Into a 300 m1. Monel autoclave containing 100 g. (0.32 mole) of l,2-dibromoperliuoropropane and cooled to -75 C., 224 g. (1.49 moles) of perfiuoropropene were condensed in vacuo. The autoclave was sealed and 4.04 (197.8 11.). 282 m of a known concentration in isooctane, 2,3,3-triheated at a temperature of 255 C. with shaking for 560 hours. The pressure dropped from 4100 to 1675 p.s.i. during this time. From this reaction there were recovered, by condensation in refrigerated receivers during venting of the autoclave, 40 g. of the olefin, and, by careful fractionation of the less volatile reaction products, 55 g. of the reactant dibromide and 120 g. of a brominefree fluorocarbon, B.P. 44-45" C., perfluoro(dimethylcyclobutane). By means of fractional distillation of the remaining liquid reaction products, the telorner bromides, CF BrCF(CF [CF CF(CF Br, were obtained in the following respective conversions and yields: 30% and 60% where n=l, a liquid (45 g.), middle cut, B.P. C. at mum, 1.3448; Analysis.-Calculatcd for C F Br C, 15.7, F, 49.7. Found: C, 15.8, F, 50.2; 15% and 30% where n:2, a liquid (30 g.), middle cut, B.P. 78 C. at 9 mm., 1.3435; Analysis.--Calculated for C F Br C, 17.8, F, 56.2. Found: C, 17.8, F, 56.6; 5% and 10% where 11:3.5 av. (containing n=35), a moderately viscous liquid (15 g.), middle cut, B.P. 4849 C. at ca. 0.1 mm., n 1.3423; Analysis.-Calculated for C13 5F2 Bl'2Z C, F, 61.5. Found: C, F, 61.5. A small residue (11:6 estd.) remained undistilled.

EXAMPLE XVI The procedure of Example XV is repeated using 0.32 mole of Br and 1.81 moles of perfiuoropropene. The telogen CF BrCF(CF )Br is formed in situ and the ultimate products are substantially those obtained in Example XV.

EXAMPLE XVII The procedure of Example I was carried out using C 1 and C F CFICF in the molar ratio The reaction was carried out at 200 C. for 21.5 hours. The pressure fell from 2400 p.s.i.g. at the outset, to 1950 p.s.i.g. at the end of the run. A 23% conversion was obtained comprising the following fractions:

(a) C F CF(CF )(C F 1-79% on the weight of total product.

on the of total product.

EXAMPLE XVIII A 2700 ml. stainless steel autoclave was charged with 875 g. (2.96 moles) of l-iodoperfluoropropane and 2233 g. (14.85 moles) of perfluoropropene. The autoclave was then closed and heated with shaking at 180-l90 C. for 65 hours and at 203 C. for an additional 48 hours. During this period, the pressure dropped from 5000 p.s.i. to 3100 p.s.i. The autoclave was next repressured with 225 g. (1.5 moles) of perfluoropropene and kept at 203 11 C. for 111 hours. The pressure drop was from 4550 to 3150 p.s.i. There were recovered 132 g. of C F I and about 1650 g. of perfiuoropropene. There were isolated 1520 g. of telomer, C F [CF CF(CF I, consisting of 449 g. (11:1); 407 g. (11:2); 467 g. (71:3); 44 g. (n=4); 151 g. (n =-10).

EXAMPLE XIX The procedure of Example I 'was carried out using 100 g. (0.224 mole) of C F CFICF and 310 g. (2.07 moles) of perfiuoro-propene. The reaction was carried out at 204 C. for 137 hours. p.s.i.g. at the outset to 4800 p.s.i.g. at the end of the run. The following telomer fractions were isolated:

were n=1 and 2 (21 g.) and where n:310 (140 g.). 74 g. of the last fraction (n=5l0) was a balsam-like solid.

EXAMPLE XX A 2700 ml. stainless steel autoclave was charged with 883 g. of 2-iodoperfiuorohexane and 2450 g. of perfiuoropropene. The autoclave was heated with shaking at 180-l90 C. for 48 hours, (pressure changed from 6500 to 5500 p.s.i.) and then at ZOO-203 C. for 233 hours (pressure changed from 5500 to 3800 p.s.i.). About 1800 g. of perfluoropropene and 150 g. of 2-iodoperfluorohexane were recovered. There was isolated about 1310 g. of telomer, C F- [CF CF(CF )],,I consisting of 1000 g.. (n=25); 185 g. (n=57); and 120 g. (n=7l0).

EXAMPLE XXI The procedure of Example I was repeated using G3F7(C FzOFhI as the telogen. The ratio CF; C Fu:CaF7(CFz( 1F)2I was 7.47. The reaction was conducted at 200 C. for 144 hours. Initial pressure was 3400 p.s.i.g.; final pressure, 1700 p.s.i.g. A conversion of about 80% was obtained comprising about 50% by weight of product having less than 4 (C F units per molecule and about 50% by weight having 4 or more --(C F units per molecule.

EXAMPLE XXII The procedure of Example I was carried out using 100 g. (0.168 mole) of C F [CF CF(CF I and 325 g. (2.16 moles) of perfiuoropropene. The reaction was carried out at 192-200" C. for 137 hours. The pressure fell from 10,700 p.s.i.g. at the outset to 5950 p.s.i.g. at the end of the run. There were isolated from the 182 g. of product, the following telomer fractions having the general formula C F-,[CF CF(CF ],,I:

(1) n=3-5, 84 g. (2) n=612, 58 g., B.P. 140-190 C. at 01 mm. (3) n=1315, 40 g., residue boiling above 190 C. at

Fractions (2) and (3) were transparent, friable solids.

EXAMPLE XXIII The procedure of Example I was repeated using CF I as the telogen. The mole ratio C3Fs;CF3I was 4.64. The reaction was conducted at 200 C. for 113 hours. The initial pressure was 3500 p.s.i.g. falling to 1800 p.s.i.g. at the end of the run. A conversion of 68% was obtained, to give the following products:

(a) CF (C F )I-48% by weight. This fraction boiled at 64 C. at 760 mm. and had a refractive index n =1.3282. Analysis showed C=13.8, F=49.6 per- The pressure fell from 9000' 12 cent by weight. Calculated for this compound, C=13.9, 1 :49.4.

(b) CF (C F I-22% by weight. This fraction boiled at 64 C. at 71 mm. and had a refractive index n :1.3322. Analysis showed C=17.1, 1 :57.3 percent by weight. Calculated for this telomer, C=17.0, F 57.5.

(c) CF (C F ll7% by weight. This fraction boiled at 73 C. at mm. and had a refractive index n =l.3350. Analysis showed C=l8.8, F=6l.8. Calculated for this telomer C:l7.0; 1 :57.5.

(d) A fourth fraction had an average of about five --C F groups. It was about 13% of the total product.

EXAMPLE XXIV The procedure of Example XXIII was carried out using a C F :CF I ratio of 5.43. The reaction was carried out at 194 C. for 122 hours. The initial pressure was 4150 p.s.i.g. falling to 2800 p.s.i.g. at the end of the reaction. A conversion of about 51% was obtained, the product comprising 47% by weight CF (C F )I, 23% CF3(C3F5)2I, CF3(C3F3)3I, CF3(C3F6)4I and 4% of material having an average of eight -('C F groups per molecule.

The telomer CF (C F I boiled at C. at 10 mm. and had an index of refraction n =l.3368. Analysis showed C=l9.8, F =64.4 percent by weight. Calculated for this telomer, C=l9.6, F=64.4 percent by weight.

The material, having an average of eight --(C F units contained a fraction having an average of 9 olefin units, a fraction having an average of 11 olefin units and a fraction having an average of 15 olefin units.

The fraction having an average of 9 units melted at 35-42 C., boiled at -150 C. at ca. 0.1 mm. and had an index of refraction, n =1.3358. Analysis showed C=2l.7, F=70% by weight. Calculated C=21.8, F=70.0%.

The fraction having an average of 11 olefin units boiled at 150-170 C. at ca. 0.1 mm. and melted at 47-56 C. It had an index of refraction, n 1.3357. Analysis showed C=22.2% by weight. Calculated C=22.l, 1 :71.0.

The fraction having an average of 15 olefin units had a melting point of 68-76 C.

EXAMPLE XXV Forty-two grams (0.20 mole) of dib-rornodifluoromethane and 151 g. (1.01 moles) of perfiuoropropene were condensed in vacuo in a cc. Monel autoclave cooled in Dry Ice. The autoclave was sealed and heated at a temperature of 245 C. for 10 days while shaking. During this period the pressure dropped from 4000 to 1700 p.s.i., about one-half of the drop occurring during the first day.

From this reaction there were recovered by venting through refrigerated receivers 75 g. of perfiuoropropene, 4 g. of dibromodifluoromethaneand 4 g. of perfluoro(dimethylcyclobutane). The remaining liquid products were rectified in a small Vigreux still. The resulting fractions were shown by their infrared spectra to consist entirely of telomer bromides, BrCF [CF CF(CF Br, which may be regarded as homologues of the telomer bromide series Br[CF CF(CF Br derived from described previously. Thus, with values of n estimated by comparison with the latter series, the composition of the remaining products was found to be 20 (weight)% n=1 av., B.P. mainly 40-50 C./100 mm., 20% 21:2 av., B.P. mainly 9395 C./100 mm., 20% n=3 av., B.P. mainly 80-87 C./8 mm., 15% n=4 av., B.P. mainly 45-55 C./ca. 0.1 mm. and 10% 11:5 av. (containing n=46) B.P. 55-l24 C./ca. 0.1 mm. For an intermediate fraction, B.P. 82-114 C./8 mm., n=3.5 av., the following values were determined: viscosities, 13.46

cs. (centistokes) at 784 1 7.3 cs. at 100 F. (extrapolated), 4.33 cs. at 123.8" E, 1.48 cs. at 197.6 F. and 1.3 cs. at 210 F. (extrapolzted), ASTM slope (78-198" F.), 1.26; c1 2.1312. For a fraction, B.P. 78-124/ca. 0.1 mm., n=5+ viscosities were 13,190 cs. at 78.4 F., 1400 cs. at 100 F. (extrapolated), 240 cs. at 123.8 F., 11.8 cs. at 197.6 F. and 8.6 cs. at 210 F. (extrapolated), ASTM slope (78-198 F.), 1.29.

EXAMPLE XXVI A 300 cc. Monel autoclave was cooled to -75 C. and evacuated. Seventy five grams (0.50 mole) of bromotrifluorornethane and 300 g. (2.0 moles) of perfluoropropene were condensed in the autoclave by gaseous transfer. The reaction mixture was shaken and heated finally at a temperature of 260 C. for 296 hours. During this time the pressure dropped from 9000 to 5600 p.s.i. After cooling to room temperature, the autoclave was vented slowly through a series of refrigerated receivers at atmospheric pressure. Recovered from the Dry Ice-cooled receivers were 60 g. of bromotrifluoromethane and 110 g. of perfluoropropene. Collected from the brine-cooled receivers and the autoclave were 200 g. of higher boiling liquid which was carefully fractionated. By this means there were obtained 155 g. of perfluoro(dimethylcyclobutane). and about 10 g. of CF CF CFBrCF (estimated by vapor-liquid chromatography.) A fraction (11 g.) B.P. 119-121 C. middle cut 121 C., colorless liquid, n 1.3044 was CF [CF CF(CF Br where n=2. Analysis-Calculated for C1F Br: F, 63.5, Br, 17.8. Found: F, 63.3, Br, 17.0. The telomer bromide where 71:3 was collected as a fraction (10.5 g.) middle cut, B.P. 93 C. at 50 mm, colorless liquid, 11 1.3139. Analysis-Calculated for C F Br: C, 20.1; F, 66.6, Br, 13.3. Found: C, 20.6, F, 67.1, Br, 12.7. The remaining fraction g.) B.P. 51-160 C. at ca. 0.1 mm. was n=ca. 5.5 av. (estimated) containing n=47. The last portion of this fraction became solid at room temperature. Finally, a residue of higher telorner, 1 g. remained undistilled.

EXAMPLE XXVII A Monel autoclave was charged with 65.0 g. of l-iodoperfluoropropane, and 95 g. of 2,3,3,3-tetrafluoropropene- 1 (CF CF:CH was then added by vacuum transfer. The autoclave was heated with shaking at 187-190 C. for 89 hours. The pressure fell from 1100 p.s.i. at the outset to 150 p.s.i. at the end of the run. There were recovered 45 g. of the tetraiiuoropropene and 15.9 g. of l-iodoperfiuoropropane. The total of 88.2 g. of produce, C F [CH CF(CF ],,I wherein n was 1-10 av., was separated into various fractions by rectification. The lower boiling fractions (ca. 33 g.) boiled mostly at 80- 122 C. at 18 mm. The higher boiling fractions were:

(a) 12 g.B.P., 84-104" C. (0.1 mm), n :1.3503.

(b) 7.8 g.B.l., 104-110 C. (0.1 mm), n :1.35l8.

(c) 13.7 g.B.P., 122-137 C. 01 mm), 11

(d) 7.2 g.-B.P., 137-170 S. 0.1 111111.), #113385:

(e) 2.5 g. residue.

Fractions (a) to (d) ranged from a light oil to a very heavy oil. Residue (e) was a solid.

The ultra-violet spectra maxima in isooctane were mostly at 272-274 nut. The infra-red spectra of all of the samples were nearly identical. They all had bands at 3.3 (CHstretching). Strong hands were present at 7.4-9.0 (CF stretching), 10.8 1, 12.6 1 and a doublet, 13.48 and 13.65 ,11.

Telomers of 2,3,3,3-tetrafiuoropropene-1 and their manufacture are described and claimed in our copending application Serial No. 251,073, filed January 14, 1963, which is a continuation-in-part of this application.

1 EXAMPLE XXVIlI A Monel autoclave was charged with 24.0 g. of 1- iodoperfluoropropane and 54.5 g. of perfluorobutadiene. The autoclave was heated with shaking at 210 C. for 16 hours. The pressure fell from 600 p.s.i.g. at the outset to zero p.s.i.g. at the end of the run. There were recovered 33.7 g. of perfluorobutadiene and 4 g. of l-iodoperfluoropropane. There was collected 37.0 g. of a product A" ranging from a light oil to a heavy oil and waxy solid. A 16 g. aliquot of product A" was fractionally distilled. Approximately /3 of the material boiled at 41-128 C. at 68 mm. and a at 58-190" C. at below 0.1 mm. The ultra-violet spectra of these samples had maxima in isooctane at about 270 mu.

EXAMPLE XXIX The procedure of Example XXVIII was carried out using 20 g. of product A from Example XXVIII and 36.7 g. of perfluorobutadiene. The reaction was carried out at 210 C. for 5 days. There were recovered 18.8 g. of perfluorobutadiene. The total of 27 g. of product was separated into various fractions by rectification. The three highest boiling fractions were (a) 7.2 g.B.P., 42-105 C. (0.1 mm), n =1.3589

EXAMPLE XXX A Monel autoclave was charged with 120 g. of l-i odopertluoropropane and 262 g. of Perfiuorocyclohutene. The autoclave was heated with shaking at 210270 C. for 72 hours. The pressure fell from 4800 p.s.i. (210 C.- at the outset to 3050 p.s.i. (210 C.) at the end of the run. There were recovered approximately 150 g. of perfiuorocyclobutene and 35 g. of l-iodoperfluoropropane. There was collected 187 g. of product containing This was separated into the following fractions by rectification:

1 55.4 g.-B.P., 35-s7 c. 100 mm.), n :1.3338 2 14.7 g.-B.P., 87-95 c. 100 mm.), 12D2:1.3418 3 10.9 g.-B.P., -110 c. mm.), n =1.3419 4 10.2 B.P., -125 c. 100 mm.), n;{-"=1.3462 5 27.1 g.-B.P., 7048 c. 0.1 mm), 513500 (6) 32.7 g.-B.P., 100-146" c. 0.1 mm.), -E1354 7 18.8 g.-B.P., 146-165" c. 0.1 m1n.),n =1.3588

(8) 1.9 g.-B.P., -180" C. (0.1 mm), 1z =1.3558

Fractions (1) and (2) contained C lTGF-GF tr CFz- FL] Fractions (3) and (4) contained C=F-,[:(|3F-(FF I GFrcFzl is Fractions (5) to (8) contained higher telomers having up to 10 perfiuorocyclobutene units. There was also a small residue containing from 10 to 20 olefin units. Fractrons (6) and (7) were medium to heavy oils. Fraction (8) was a waxy solid with pour point at about 27-30 C. The ultra-violet spectra maxima in isooctane were at about 270 run. The infra-red spectra of fractions (5) to (8) were almost identical. The appearance of bonds at 5.62 and 5.84 m (double bond region) in these spectra which were also found in the perfiuorobutadiene reactions (Examples XXVHI and XXIX) suggest that at least 15 some rearrangement of perfiuorocyclobutene to perfluorobutadiene occurred during the thermal reaction and that thegross product was not pure telomer.

EXAMPLE XXXI Perfiuorocyclobutene (202 g.) was transferred in vacuum to a 300 ml. Monel autoclave which contained 265 g. 1,2-dichloro-1,1,2-trifiuoroiodoethane. The autoclave was sealed and heated in a shaking apparatus for 158 hours at 225 C. There was a pressure drop from about 5250 p.s.i.g., which was noted when the temperature reached 225 C., to 3825 p.s.i.g. when the heating was discontinued. The autoclave was cooled to room temperature and vented. The residual contents were filtered to remove a small amount of iodine and the filtrate was distilled. Unreacted CF CICFCII was removed at a pressure of 80 mm. Hg at 37-45 C. The remaining liquid was fractionated to yield 50 g.

boiling at 6l-66 C. (23 mm. Hg) n 1.4073; 14.4 g.

boiling at 7379 C. (5 to 6 mm. Hg) zz 1.3963, Analysis of the low boiling fraction showed 16.6% C, 0.0% H, 28.4% I; calculated for C CI F I: 16.3% C, 0.0% H, 28.8% I. Analysis of the high boiling fraction showed 19.4% C, 0.0% H, calculated for C Cl F I: 19.9% C, 0.0 H. There was left in the distilling flask 6 g. of viscous oil consisting of higher telomers,

where n=3 and 4.

The 1:1 adduct described above, 1-(1,2-dichloro-1,2,2- trifiuoroethyl)-2-iodohexafiuorocyclobutane, is claimed in our copending application Serial No. 250,761, filed January 11, 1963, which is a continuation-in-part of this application.

EXAMPLE XXXII A 300 ml. Monel autoclave filled with Monel balls to reduce the elfective volume to 150 ml. was charged with 50 g. of CF ClCFClI and 75 g. of perfiuoropropene and heated for 112 hours at 172-197 C. in a molten salt bath and then for 15.5 hours in a shaker at 201 C. during this period the pressure dropped from 950 p.s.i. at 172 C. to 750 p.s.i. at 201 C. At this time an additional g. of perfluoropropene was charged into the autoclave 1 3 which was heated for 40 hours more at 201 C. Seventy grams of olefin and 15 g. of CF ClCFClI were recovered. Rectification of the remaining product,

in vacuo gave the following fractions:

(a) 11:1 (25 g.) B.P. mostly 58.5-60.5" C. at 20 mm., n =l.3908. Analysis showed C=14.5% by weight. Calculated C=14.0% by weight.

(b) n=2 (15 g.) B.P. mostly 97.5-104" C. at 20 mm. n =1.376O. Analysis showed C=l6.8% by weight. Calculated C=16.6%.

(c) n=3 average (7 g.) B.P. mostly 7787 C. at ca. 0.1 mm. n =1.3706.

(d) n=4 average (4 g.) B.P. 87-138 C. at ca. 0.1 mm., n =1.3691. Analysis showed C=l9.0% by weight. Calculated C=19.l%.

Under conditions similar to those used in Example X, products having up to 10 olefin units per molecule may be obtained.

EXAMPLE XXXIII CH LORINATION OF TELOMER A 300 ml. Monel autoclave was charged with 200 g. (0.335 mole) of C F [CF CF(CF 1 1, sealed, and cooled to -78 C. Seventy-five grams of chlorine (1.055 moles) were admitted to the autoclave which was then heated with shaking at 203 C. for 17 hours.

Excess chlorine was vented from the autoclave and the remaining material was washed with water, 10% aqueous caustic solution, and Water, then dried and distilled. (With higher telomers CF ClCFCl solvent was used to reduce the viscosity during washing, etc.) There were obtained 150 g. (0.297 mole) of chlorinated product, C F [CF CF(CF Cl representing an 89% yield.

Yields of 85l00% were obtained by chlorination of the other telomer iodides. Some physical properties of the series C F [CF CF(CF CI are listed in Tables III and IV.

EXAMPLE XXXIV FLUORINATION OF TELOMER Into a 2-liter Monel metal round-bottom flask equipped with a steel wire Hershberger stirrer and a copper, watercooied condenser were charged 418 g. (0.350 mole) of a mixture of fluorocarbon iodides,

trifiuoride. The mixture was heated with stirring to 190 C. during 1.5 hours and the temperature was maintained at Table III PHYSICAL (JONSTANTS 0F STABILIZED TELOMERS Boiling point Analysis T Pour llmmt C 1) F1 1 cm or me ting ar an, percent uor ne, Formula 71D point, 0. percent.

C. Mm. Hg

Cale. Found Cale. Found C3F7[CFQCF(CF3)]|C1 82 760 1. 2826 26 80 20. 3 20.0 69. 7 69. 8 C 1T [CF:CFCF )J;C1 134 760 1. 299 22 80 21. 4 21. 7 71. 5 71. 8 C FHFJIHCF C1 C] 8 1.3091 22 22.0 22.0 72.6 C1 F (31 01 701 3) 10 112 10 1.3169 20 Ca. 15 22.4 22.8 73.2 73.8 C3I* [CF,CF( CF 010 66 96 0.1 1.3172 30 Ca. 10 22. 6 22.6 73. 6 73. 7 C FAOF OFUJFQ C1 06-117 0.1 1.3205 31 Ca. 25 22.8 22. 6 74. 0 73. 7 CEFACF CNCFZ) HMO] 117-150 0.1 Soiid 38-42 23.1 23.1 74. 4 74. 4 C FACFZCMCFB) VOL. 150470 0.1 Solid 5840 23.2 23. 0 74. 5 74. 6 C3F7I CF3CF(CF3) xF-- 115410 98 1.290 30 Ca. 40 22.6 22.7 77.4 77. B C F [CF CF(CF F" 143115 1. 3003 30 Ca. 10 22. 9 22. 8 77.1 77.3 C;F [CF,CF(CF3) .sF.. 173 95 1. 3067 30 (3a. 15 23.0 22.8 77.0 77. 1 CaF'; CFCF(CF;) F 84-143 Ca. 0.1 1. 3112 29 Ca. 20 23. 2 23.0 76.8 76.9 0 F? CF7GF(CF:|) 9..,F -180 01 Solid 5864 23. 5 23.5 76.5 76.7 C F [CF,CF(CF )]1 .,,F 165-210 0. 1 1. 314 27 71-75 1 Estimated.

Table IV Kinematic Vlsoosities (Centistokes) of Stabilized 'Ielomers Formula 78.4 F. 141.4 F. 197.8" F. 100 F. 210 in ASTM slope b CaF7% I F(CF3) 101 1. 421 0.608 0. 461 0. 65 0. 35 1.4.6 03F: CFzCFlCFs) 301. 4. as 2.07 0. 397 2. 9s 0. s13 1.33 ctFil Fi Fw ohcl. 43.11 8.13 2. 003 17. a 1. 74 1.34 3F'i[ I F(CF3)]snvC 1 s7. 5. 66 210 4. 55 1. 2s CtFvl FicFt Fhlmol. 610. or 10.40 5,100 11.9 1. a4 3 7i 2 F( F3HxAvF 3. 58 1.47 0.79 2. s5 0. 46 1. 3'1 7i 2 FsHH-F 36.75 4.71 1.84 15.0 1.00 1. as Ti I 3)]B.-W 501.97 9.11 6,300 e. 5 1.04

Extrapolated. viscosity chart. The ASTM slope is the slope at this line showing the (9 min); pour point, 21 0., Ns25=l.303l.

At123s F.

230-250 C. for several hours. The reaction mixture was then cooled, a fresh 100 g. portion (0.86 mole) of cobalt trifluoride was added and heating was resumed at 230 C. for two additional hours. After cooling, :1 copper distillation head and receiver were substituted for the condenser, the flask was heated, and the pressure was reduced to ca. 0.1 mm. to allow the crude product, 291.5 g. (76.5% of theory), to be distilled. The final pot temperature reached during distillation was 275 C. The crude product was taken up in CF ClCFCl to reduce the viscosity and washed with dilute hydrochloric acid, dilute caustic, and finally water, and then dried. Rectification through a Vigreux still was employed to separate components of various n values. Constants and physical properties of some members of this series, C F [CF CF(CF )],-,F are listed in Tables III and IV.

EXAMPLE XXX V FLUORINA'IION OF 2-10110PERFLUGROIIEXANE Cobalt trifluoride (60 g.) supported on copper shot was placed in a vertical copper tube, which was surrounded by a tube furnace. 2-iodoperfiuorohexane g., 0.0448 mole) was added drop by drop on top of the cobalt triiiuoride under a dry nitrogen atmosphere at 260-290 C. The exit gases were condensed in a Dry Ice-cooled trap, washed with 5% sodium hydroxide (some handling losses occurred), dried with Drierite and distilled to give only n-perfiuorohexane (75%), B.P. 54 C., as shown by its infra-red spectrum.

EXAMPLE XXXVI STABILIZATION BY HEATING A 2.7 l. 316 stainless steel autoclave was charged with 875 g. of iodoperfiuoropropane and 2050 g. of perfiuoropropene and then heated at 200 C. for 60 hours with continuous shaking. The temperature was then allowed to rise to about 300305 C. for several hours. From this reaction were recovered 1355 g. of perfluoropropene, ca. 65 g. of iodine, and 1360 g. of higher boiling products. The latter were shown to be composed of iodinefree stabilized fluorocarbon materials in addition to the usual telomer iodides. Fractionation of this material by means of a 1 inch diameter by 1 foot glass helices-packed column was used to separate 667 g. of 2-iodoperfluorohexane. The remaining 693 g. of product (ranging from oils to solids) boiling from 100 C. at 100 mm. to ll0 C. ca. 0.1 mm. consisted of approximately 20% by weight of perfluoro-S, 6-dimethyldecane, of higher coupling products, and 55% of higher telomer iodides.

EXAMPLE XXXVII Strips of polymerized tetrafiuoroethylene, V thick and A" wide, were heated at 310 C. in both These latter compounds were oils having distillation ranges of 84-143 C. at (0.1 mm. and 96-117 C.

b The viscosity valves lie on a straight line when plotted on an ASTM (D341-43) temperature dependence of viscosity. 0 Distillation range 6747 G. (9 min); pour point, about ll0 0., N.,2 3=1.292.

Distillation range 77-126 at 0.1 1pm., respectively. After about 4 hours the strips were removed from the oil and wiped thoroughly. The strips were about 20% heavier and noticeably softer and more pliable.

EXAMPLE XXXVIII A polytetrafluoroediylene tape, 5 mils thick and 0.1 inch wide was immersed in C3F7[CF2CF(CF3)]3 C1 at C. overnight. After removal of excess chloride by drainage, the plasticized strip was tested in an lnstrom tester for percent elongation and tensile strength. It was found that the original unplasticized strip broke under a load of 2.6 lbs. and gave an elongation of The plasticized strip broke under a load of 3.7 lbs. and gave an elongation of 410%.

Similar results were obtained using as well as the coupling product {C F-;[CF CF(CF Thus by using the products of the present invention a greatly improved polytetrafiuoroethylene tape can be obtained, useful, for example, in insulating wires. In particular, use of the present invention overcomes the lack of elasticity and strength hitherto considered inherent in polytetrafiuoroethylene tapes.

EXAMPLE XXXIX One half gram of C F [CF CF(CF I was diluted with acetone to give a 10% solution. This solution was further diluted to 1% with a sterile soap solution. Using the standard FDA Phenol Coefiicient Test, the 1% solution was found to prevent the growth of Salmonella typhosa (Hopkins) and Micrococcus pyrogenes var. aureaus No. 209. The Germicide-Agar Dilution Test, a standard bacteriostatic test, also showed that a 1% solution of the above compound prevents growth of the two organisms referred to.

What is claimed is:

l. A polymeric product having the general formula R(U),,Q where Q is a halogen atom, R is selected from the group consisting of perfluoroalkyl, perfluorocycloalkyl, and perfiuoroalkenyl radicals; and perfluorochloroalkyl, perfiuorohydroalkyl, perfluorochlorocycloalkyl, perfluorohydrocycloalkyl, perfiuorochloroalkenyl, and perfluorohydroalkenyl radicals in which the carbon atom nearest to the Q atom has at least one substituent selected from the group consisting of halogen, perfiuoroalkyl radicals and R'cF -radicals where R is selected from the group consisting of perfluorochloroalkyl and perfluorohydro-alkyl radicals, U is a bifunctional group derived from a perfluorinated unsaturated compound selected from the group consisting of perfiuorobutadiene, perfluorocyclobutene, and olefins having the formula 8 carbon atoms, and n is a number at least equal to 3.

2. The product claimed in claim 1 wherein R is a 19 perfiuoroalkyl group and U is derived from perfluoropropene.

3. Compounds having the general formula where Q is a halogen atom and n is from 3 to about 20.

4. Compounds having the general formula where Q is a halogen atom and n is from 3 to about 20.

5. Compounds having the general formula where Q is a halogen atom and n is an integer from 3 to about 20.

6. Compounds having the general formula where Q is a halogen atom and n is an integer from 3 to about 20.

7. Compounds having the general formula where Q is a halogen atom and n is from 3 to about 20.

8. Compounds having the general formula 03!; OF-OF Q I: F8 F! u where Q is a halogen atom and n is from 3 to about 20.

9. A method for producing organic fluorinated compounds which comprises heating, at a temperature between about 160 C. and about 350 C., a telogen having the general formula RI, where R is selected from the group consisting of perfluoroalkyl, perfluorocycloalkyl and perfluoroalkenyl radicals; and perfluorochloroalkyl, perfluorohydroalkyl, perfluorochloroeycloalkyl, perfluorohydrocycloalkyl, perfluorochloroalkenyl and perfluorohydroalkenyl radicals in which the carbon atom which is attached to the iodine atom has at least one substituent selected from the group consisting of halogen, perfluoroalkyl radicals and R'CF -radicals Where R is selected from the group consisting of perfiuorochloroalkyl and perfluorohydroalkyl radicals, with an unsaturated, fluorinated compound selected from the group consisting of compounds having the formula R"--CF=CF where R" is a perfiuoroalkyl group having not more than 8 carbon atoms, perfluorobutacliene and perfiuorocyclobutene, the molar ratio of unsaturated compound to telogen being between about 2: 1 and about 20:1.

10. The method claimed in claim 9 wherein the telogen is a perfluoroalkyl iodide and the unsaturated compound is perfluoropropene.

11. The method claimed in claim 9 wherein the telogen is formed in situ by reaction of the unsaturated compound with a halogenating agent selected from the group consisting of I; and 1C].

References Cited in the file of this patent UNITED STATES PATENTS 2,440,800 Hanford et a1 May 4, 1948 2,875,253 Barnhart Feb. 24, 1959 2,880,247 Miller Mar. 31, 1959 2,880,248 Miller Mar. 31, 1959 OTHER REFERENCES Henne et al.: Jour. Am. Chem. Soc., vol. 73, pp. 1791 and 1792, April 1951.

Haszeldine: Jour. Chem. Soc., July 1952, pp. 2504- 2513 (only pp. 2510 and 2511 necessary).

Haszeldine et al.: Jour. Chem. Soc., April 1953, pp. 11994206.

Haszeldine et al.: Jour. Chem. Soc., May 1953, pp. 1592-1600.

Haszeldine: Jour. Chem. Soc., December 1955, pp. 4291-4302. 

1. A POLYMERIC PRODUCT HAVING THE GENERAL FORMULA R(U)NQ WHERE Q IS A HALOGEN ATOM, R IS SELECTED FROM THE GROUP CONSISTING OF PERFLUOROALKYL, PERFLUOROCYCLOALKYL, AND PERFLUOROALKENYL RADICALS; AND PERFLUOROCHLOROALKYL, PERFLUOROHYDROALKYL, PERFLUOROCHLOROCYCLOALKYL, PERFLUOROHYDROCYCLOALKYL, PERFLUOROCHLOROALKENYL, AND PERFLUOROHYDROALKENYL RADICALS IN WHICH THE CARBON ATOM NEAREST TO THE Q ATOM HAS AT LEAST ONE SUBSTITUENT SELECTED FROM THE GROUP CONSISTING OF HALOGEN, PERFLUOROALKYL RADICALS AND R''CF2-RADICALS WHERE R'' IS SELECTED FROM THE GROUP CONSISTING OF PERFLUOROHLOROALKYL AND PERFLUOROHYDROALKYL RADICALS, U IS A BIFUNCTIONAL GROUP DERIVED FROM A PERFLUORINATED UNSATURATED COMPOUND SELECTED FROM THE GROUP CONSISTING OF PERFLUOROBUTADIENE, PERFLUOROCYCLOBUTENE, AND OLEFINS HAVING THE FORMULA 